CN108299666B - Preparation method of microvascular self-repairing coating - Google Patents
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Abstract
The invention discloses a preparation method of a microvascular self-repairing coating, the coating prepared by the method is composed of a bottom coating and a surface coating, a microvascular network is constructed in the bottom coating, a repairing agent is injected into the bottom coating, and a curing agent is added into the surface coating. When the surface layer coating is damaged, the repairing agent overflows from the damaged position through the capillary network and reacts with the curing agent in the surface layer coating to heal the damage. The microvascular network system constructed by the invention is composed of an aorta and capillaries, wherein the aorta has large diameter, large storage capacity of a repairing agent and deep implantation, and is not easy to damage; the capillary vessels have small diameter, relatively dense arrangement and shallow implantation, and are easy to be damaged synchronously with the surface coating; the coating is guaranteed to have higher repairing efficiency, and multiple times of repairing at the same position can be realized.
Description
Technical Field
The invention belongs to the field of self-repairing polymer materials, and particularly relates to a preparation method of a microvascular self-repairing coating.
Background
The polymer is easy to age under the action of environment and load, and microcracks are generated on the surface and inside of the polymer, so that the service performance of the material is reduced, and the service life of the material is shortened. If the micro-crack of the polymer can be automatically repaired and prevented from being damaged, the service life of the polymer can be prolonged and the use safety and reliability of the polymer can be improved. Self-repairing polymer materials were proposed in the 70 s of the 20 th century, and through more than 40 years of development, various methods for repairing cracks appeared in sequence: (1) repairing by utilizing intermolecular interaction; (2) repairing by utilizing a thermal reversible crosslinking reaction; (3) self-repairing by using a liquid core fiber method; (4) and (3) performing bionic self-repairing by using a microcapsule method. The self-repairing method of utilizing intermolecular interaction and thermal reversible crosslinking reaction needs to provide external repairing environments such as certain temperature and the like, and timely repairing of microcracks is difficult to achieve; the liquid core fiber method and the microcapsule method cannot realize multiple times of repair of the same position of the matrix because the storage amount of the repair agent is limited and the repair agent is relatively and fixedly distributed in the matrix.
In 2001, DCPD-UF microcapsules were first prepared in s.r. white and added to the EP matrix together with the Grubbs catalyst in powder form. When the microcapsules are destroyed by the microcracks, the DCPD is released to the crack sites and contacts with the catalyst to initiate the ring-opening polymerization reaction and bond the cracks together. Then, e.n.brown, m.w.keller, b.j.blaiszik, k.s.toohey, a.r.hamilton, m.baginska, etc. performed systematic research work in this field, and obtained many valuable research results. In order to realize the repeated repair of the self-repairing material, on the basis of the microcapsule self-repairing composite material, K.S. Toohey et al develop the research of the microvascular network self-repairing coating. The bionic coating-substrate has the structure as follows: implanting the three-dimensional microvascular network filled with the repairing agent into a base material, wherein the thickness of the base material adopted in the experiment is 5-7mm and the base material has certain toughness, and then coating a layer of brittle coating which is 500-800 mu m thick and contains the catalyst on the surface of the base material. When the material is damaged, the brittle coating firstly generates cracks, and the repair monomer enters the damaged surface through the conveying of the microvasculature and reacts with the catalyst in the coating to repair the cracks. Studies have shown that for a single crack resulting from EP coating, the microcapsule coating can only be repaired once, while the microvasculature can be repaired up to seven times. Therefore, the three-dimensional microvascular network self-repairing method can repair the substrate material for multiple times and has the advantages which are not possessed by other methods.
The three-dimensional microvascular network reported by k.s.tohey et al adopts 3D printing technology, completes the preparation of microvascular by taking paraffin as a material, then implants the microvascular into a matrix material, and then forms a three-dimensional network structure after heating and removing the paraffin. In practical application, however, the cost of the paraffin three-dimensional microvessels printed by 3D is high, the transplantation is difficult, and the liquid paraffin is difficult to clean, so that the popularization and the application of the microvessel self-repairing coating are not facilitated.
Disclosure of Invention
In order to solve the problems in the prior art, the invention discloses a preparation method of a microvascular self-repairing coating. The microvascular self-repairing coating can realize multiple times of repairing of the same position of a coating material, is applied to the surface of a workpiece which is inconvenient to maintain or has higher maintenance cost, and can effectively prolong the service life of the workpiece and reduce the comprehensive application cost.
In order to achieve the purpose, the invention adopts the technical scheme that the preparation method of the microvascular self-repairing coating comprises the following steps:
step 1, surface modification of the filler: firstly, weighing a certain mass of muscovite, heavy calcium carbonate, quartz powder and nano SiO2 as fillers, then respectively weighing a silane coupling agent KH-560 with the mass of 1.5-2% of that of the corresponding fillers, diluting the silane coupling agent KH-560 into a solution with the mass of 5-10% by using absolute ethyl alcohol, uniformly spraying the solution into the corresponding fillers under the condition of stirring, and then drying the solution at the temperature of 60 ℃ for later use;
step 2, preparing a primer: according to the mass of each component, 100 parts of epoxy resin E-44 is dissolved in 60-80 parts of acetone solvent, 9 parts of diethylenetriamine and 2-3 parts of benzyl alcohol are added after the dissolution, 150-200 parts of modified quartz powder are added after the uniform stirring, the continuous stirring is carried out for 10-15 min, 80-100 parts of modified muscovite and 200-300 parts of modified calcium carbonate are sequentially added while the stirring is carried out, 10-50 parts of acetone is added to adjust the viscosity of the system, and the bottom coating is obtained after the full and uniform stirring;
step 3, coating of a bottom layer coating and construction of a microvascular network: laying longitudinal and transverse support bars on the surface of a base material, wherein the diameter of the longitudinal support bars is 2mm, the interval is 20-30 mm, the diameter of the transverse support bars is 1mm, and the interval is 10-15 mm, then uniformly coating the bottom layer coating prepared in the step 2 on the surfaces of the base material and the support bars to form a coating with the thickness of 3-3.5 mm, then placing the coating in a drying box, keeping the temperature for 2 hours at 40 ℃, then keeping the bottom layer coating in a semi-solidified state, slowly drawing out the support bars to form hollow channels which penetrate through each other vertically and horizontally, namely a microvascular network, finally, plugging the two ends of the longitudinal channels and one end of the transverse channel with the bottom layer coating, then placing a sample in a drying box, keeping the temperature for 30min at 60 ℃ to fully solidify the bottom layer coating;
step 4, preparing and pouring a repairing agent: dissolving 100 parts of epoxy resin 618 in 10 parts of acetone, adding 5-10 parts of benzyl alcohol and 3-5 parts of pigment to prepare a repairing agent, injecting the repairing agent into the microvascular network obtained in the step 3 by using an injector, and then completely plugging the openings of the rest pore channels by using primer;
step 5, preparing and coating a surface layer coating: according to the mass of each component, 100 parts of epoxy resin E-44 is dissolved in 30-50 parts of acetone, 12-15 parts of ethylenediamine, 5-7 parts of pigment and 150-200 parts of modified nano SiO2Preparing a surface layer coating, uniformly spraying the surface layer coating on the surface of the bottom layer coating by using a spray gun to form a coating with the thickness of 0.3-0.8 mm, and naturally curing at normal temperature to obtain the surface layer coating.
The purity of the silane coupling agent KH-560 in the step 1 is analytical purity, the average grain diameter of the quartz powder and the muscovite is less than 15 mu m, and the nano SiO is2The average particle diameter of (A) is 20 to 80 nm.
The purity of the epoxy resin E-44 in the step 2 is chemical purity, and the purity of the acetone, the benzyl alcohol and the diethylenetriamine is analytical purity.
Step 4 the purity of the epoxy resin 618 is chemically pure.
The purity of the ethylenediamine in the step 5 is analytical purity.
And step 3, the supporting strips are rubber strips, iron wires or wood strips.
In the step 1, the muscovite filler is replaced by talcum powder, argil or bentonite, the heavy calcium carbonate filler is replaced by light calcium carbonate, and the quartz powder filler is replaced by titanium dioxide or fly ash.
Compared with the prior art, the invention has at least the following beneficial effects: the coating has higher repairing efficiency when damaged, and can realize multiple times of repairing at the same position. The longitudinal microvasculature has large diameter and deep implantation, and plays a role of 'aorta'; the transverse microvascular diameter is small, the implantation is shallow, the capillary function is exerted, and the applicability of the microvascular self-repairing coating is strong.
Drawings
Fig. 1 is a schematic structural diagram of a microvascular self-healing coating.
Fig. 2 is a sample of a microvascular self-healing coating.
FIG. 3 is a partial end face of a sample of a microvascular self-healing coating.
FIG. 4 is an SEM image of a coating scratch partially repaired by a repair agent.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
1. Materials, reagents and apparatus for use in the invention
1) The materials and reagents used were as follows:
muscovite, 10 μm, source rich mining, llc;
heavy calcium carbonate with an average particle size of 15 μm, from Ribo chemical Co., Ltd, Changsha;
200-mesh quartz powder, quartz sand factory in Qianshan province;
nano SiO230nm in average particle size, Zhejiang Zhoushan Mingri nanometer materials Co., Ltd;
silane coupling agent KH-560, analytically pure, Shanghai Yanghua chemical plant;
absolute ethanol, chemical purity, sienna sanpu fine chemical plant;
epoxy E-44, chemically pure, Lanzhou Lanxing resin, Inc.;
acetone, analytically pure, ningxin chemical ltd, tianjin city;
diethylenetriamine, analytically pure, guangdong Guanghong Guanghuake technology, Inc.;
benzyl alcohol, analytically pure, Tianjin, Shanghai chemical reagent factory;
rubber strips with specifications of 2mm and 1mm, Huaqi seal Limited;
epoxy resin 618, chemical purity, blue star chemical tin-free resin fine chemical research institute;
ethylenediamine, analytical grade, chemical reagents of the national drug group, ltd;
pigment, industrial grade, Yangzhou Anbang pigment chemical Co., Ltd.
2) The used equipment mainly comprises:
dry box, DHG, shanghai essence macro laboratory instruments ltd;
electronic balance, VALOR3000, shanghai asian limited;
heat collection magnetic stirrers, DF-101S, changzhou guohua appliances ltd;
spray gun, HD-130, Shenzhen crab kingdom science and technology Limited;
mini air pump, model: U-STAR, Shenzhen crab kingdom science and technology Limited;
scanning electron microscope, JSM-6390LV, JEOL Inc., Japan.
2. Main technical link for preparing microvascular self-repairing coating
Surface modification of the filler: firstly, certain mass of muscovite, heavy calcium carbonate, quartz powder and nano SiO are weighed2As a filler, respectively weighing a silane coupling agent KH-560 with the mass of 1.5-2% of that of the corresponding filler, diluting the silane coupling agent KH-560 into a solution with the mass of 5-10% by using absolute ethyl alcohol, uniformly spraying the solution into the corresponding filler under the condition of stirring, and drying at 60 ℃ for later use;
preparing a primer: according to the mass of each component, 100 parts of epoxy resin E-44 is dissolved in 60-80 parts of acetone solvent, 9 parts of diethylenetriamine and 2-3 parts of benzyl alcohol are added after the dissolution, 150-200 parts of modified quartz powder is added after the uniform stirring, and the continuous stirring is carried out for 10-15 min. While stirring, sequentially adding 80-100 parts of modified muscovite and 200-300 parts of modified calcium carbonate, adding 10-50 parts of acetone to adjust the viscosity of the system, and fully and uniformly stirring to obtain a primer;
coating of a bottom layer coating and construction of a microvascular network: laying longitudinal and transverse rubber strips on the surface of a base material, wherein the diameter of the longitudinal rubber strips is 2mm, the interval is 20-30 mm, the diameter of the transverse rubber strips is 1mm, the interval is 10-15 mm, then uniformly coating the bottom layer coating prepared in the step 2 on the surfaces of the base material and the rubber strips to form a coating with the thickness of 3-3.5 mm, then placing the coating into a drying box, keeping the temperature for 2 hours at constant temperature of 40 ℃, then keeping the bottom layer coating in a semi-curing state, slowly drawing out the rubber strips to form hollow channels which penetrate through each other vertically and horizontally, namely a microvascular network, finally, plugging the two ends of the longitudinal channels and one end of the transverse channel by using the bottom layer coating, then placing a sample into a drying box, keeping the temperature for 30min at 60 ℃ to fully cure the bottom layer coating, and further;
preparing and pouring a repairing agent: dissolving 100 parts of epoxy resin 618 in 10 parts of acetone according to the mass of each component, adding 5-10 parts of benzyl alcohol and 3-5 parts of pigment to prepare a repairing agent, injecting the repairing agent into the microvascular network obtained in the step 3 by using an injector, and then completely blocking the openings of the rest pore channels by using a coating;
preparing and coating a surface layer coating: according to the mass of each component, 100 parts of epoxy resin E-44 is dissolved in 30-50 parts of acetone, 12-15 parts of ethylenediamine, 5-7 parts of pigment and 150-200 parts of modified nano SiO2Preparing a surface layer coating, uniformly spraying the surface layer coating on the surface of the bottom layer coating by using a spray gun to form a coating with the thickness of 0.3-0.8 mm, and naturally curing at normal temperature to obtain the surface layer coating.
In the invention, the purity of the silane coupling agent KH-560 is analytically pure, the purity of the epoxy resin E-44 is chemically pure, the purity of acetone, benzyl alcohol and diethylenetriamine is analytically pure, the average particle size of quartz powder and muscovite is less than 15 mu m, the purity of the epoxy resin 618 is chemically pure, the purity of ethylenediamine is analytically pure, and the purity of nano SiO is analytically pure2The average grain diameter of the support strip is 20-80 nm, and the support strip is a rubber strip, an iron wire or a wood strip.
Example 1:
a preparation method of a microvascular self-repairing coating comprises the following steps:
step 1, surface modification of the filler: firstly, certain mass of muscovite, heavy calcium carbonate, quartz powder and nano SiO are weighed2As a filling material, respectively weighing a silane coupling agent KH-560 with the mass of 1.5% of that of the corresponding filling material, diluting the silane coupling agent KH-560 into a solution with the mass of 8% by using absolute ethyl alcohol, uniformly spraying the solution into the corresponding filling material under the condition of stirring, and drying at the temperature of 60 ℃ for later use;
step 2, preparing a primer: according to the mass of each component, 100 parts of epoxy resin E-44 is dissolved in 80 parts of acetone solvent, 9 parts of diethylenetriamine and 2 parts of benzyl alcohol are added after the dissolution, 150 parts of modified quartz powder is added after the uniform stirring, the continuous stirring is carried out for 10-15 min, 100 parts of modified muscovite and 200 parts of modified calcium carbonate are sequentially added while the stirring is carried out, 50 parts of acetone is added to adjust the viscosity of the system, and the bottom coating is obtained after the full uniform stirring;
step 3, coating of a bottom layer coating and construction of a microvascular network: laying longitudinal and transverse support bars on the surface of a base material, wherein the diameter of the longitudinal support bars is 2mm, the interval is 30mm, the diameter of the transverse support bars is 1mm, and the interval is 15mm, then uniformly coating the bottom layer coating prepared in the step 2 on the surfaces of the base material and the support bars to form a coating with the thickness of 3-3.5 mm, then placing the coating in a drying oven for keeping the temperature at 40 ℃ for 2h, keeping the coating in a semi-cured state, slowly drawing out the support bars to form hollow through holes which are penetrated vertically and horizontally, namely a microvascular network, finally, sealing and blocking the two ends of the longitudinal holes and one end of the transverse channel by using the bottom layer coating, then placing a sample in the drying oven, keeping the temperature at 60 ℃ for 30min to fully cure the bottom layer coating;
step 4, preparing and pouring a repairing agent: dissolving 100 parts of epoxy resin 618 in 10 parts of acetone according to the mass of each component, adding 10 parts of benzyl alcohol and 4 parts of pigment to prepare a repairing agent, injecting the repairing agent into the microvascular network obtained in the step 3 by using an injector, and then completely plugging the openings of the rest pores by using primer;
step 5, preparing and coating a surface layer coating: according to the mass of each component, 100 parts of epoxy resin E-44 is dissolved in 30 parts of acetone, and 15 parts of ethylenediamine, 6 parts of pigment and 170 parts of modified nano SiO are added2Preparing a surface layer coating, uniformly spraying the surface layer coating on the surface of the bottom layer coating by using a spray gun to form a coating with the thickness of 0.5mm, and naturally curing at normal temperature to obtain the surface layer coating.
Example 2:
a preparation method of a microvascular self-repairing coating comprises the following steps:
step 1, surface modification of the filler: firstly, weighing a certain mass of talcum powder, light calcium carbonate, quartz powder and sodiumSiO rice2Taking the filler as a filler, respectively weighing a silane coupling agent KH-560 with the mass of 2% of that of the corresponding filler, diluting the silane coupling agent KH-560 into a solution with the mass of 5% by using absolute ethyl alcohol, uniformly spraying the solution into the corresponding filler under the condition of stirring, and drying the solution at the temperature of 60 ℃ for later use;
step 2, preparing a primer: according to the mass of each component, 100 parts of epoxy resin E-44 is dissolved in 70 parts of acetone solvent, 9 parts of diethylenetriamine and 2 parts of benzyl alcohol are added after the dissolution, 200 parts of modified quartz powder is added after the uniform stirring, the continuous stirring is carried out for 10-15 min, 100 parts of modified muscovite and 300 parts of modified calcium carbonate are sequentially added while the stirring is carried out, 10 parts of acetone is added to adjust the viscosity of the system, and the bottom coating is obtained after the full uniform stirring;
step 3, coating of a bottom layer coating and construction of a microvascular network: laying longitudinal and transverse support bars on the surface of a base material, wherein the diameter of the longitudinal support bars is 2mm, the interval is 20mm, the diameter of the transverse support bars is 1mm, and the interval is 15mm, then uniformly coating the bottom layer coating prepared in the step 2 on the surfaces of the base material and the support bars to form a coating with the thickness of 3-3.5 mm, then placing the coating in a drying oven for keeping the temperature at 40 ℃ for 2h, keeping the coating in a semi-cured state, slowly drawing out the support bars to form hollow through holes which are penetrated vertically and horizontally, namely a microvascular network, finally, sealing and blocking the two ends of the longitudinal holes and one end of the transverse channel by using the bottom layer coating, then placing a sample in the drying oven, keeping the temperature at 60 ℃ for 30min to fully cure the bottom layer coating;
step 4, preparing and pouring a repairing agent: dissolving 100 parts of epoxy resin 618 in 10 parts of acetone according to the mass of each component, adding 8 parts of benzyl alcohol and 3 parts of pigment to prepare a repairing agent, injecting the repairing agent into the microvascular network obtained in the step 3 by using an injector, and then completely plugging the openings of the rest pores by using primer;
step 5, preparing and coating a surface layer coating: according to the mass of each component, 100 parts of epoxy resin E-44 is dissolved in 40 parts of acetone, 12 parts of ethylenediamine, 5 parts of pigment and 1570 parts of modified nano SiO are added2Preparing a surface layer coating, and uniformly spraying the surface layer coating on the surface layer coating by using a spray gunAnd forming a coating with the thickness of 0.5mm on the surface of the bottom coating, and naturally curing at normal temperature to obtain the surface coating.
Example 3:
a preparation method of a microvascular self-repairing coating comprises the following steps:
step 1, surface modification of the filler: firstly, certain mass of bentonite, heavy calcium carbonate, titanium dioxide and nano SiO are weighed2As the filler, respectively weighing a silane coupling agent KH-560 with the mass of 1.5% of that of the corresponding filler, diluting the silane coupling agent KH-560 into a solution with the mass of 5% by using absolute ethyl alcohol, uniformly spraying the solution into the corresponding filler under the condition of stirring, and drying at 60 ℃ for later use;
step 2, preparing a primer: according to the mass of each component, 100 parts of epoxy resin E-44 is dissolved in 80 parts of acetone solvent, 9 parts of diethylenetriamine and 3 parts of benzyl alcohol are added after the dissolution, 200 parts of modified quartz powder is added after the uniform stirring, the continuous stirring is carried out for 10-15 min, 90 parts of modified muscovite and 200 parts of modified calcium carbonate are sequentially added while the stirring is carried out, 30 parts of acetone is added to adjust the viscosity of the system, and the bottom coating is obtained after the full uniform stirring;
step 3, coating of a bottom layer coating and construction of a microvascular network: laying longitudinal and transverse support bars on the surface of a base material, wherein the diameter of the longitudinal support bars is 2mm, the interval is 25mm, the diameter of the transverse support bars is 1mm, and the interval is 10mm, then uniformly coating the bottom layer coating prepared in the step 2 on the surfaces of the base material and the support bars to form a coating with the thickness of 3-3.5 mm, then placing the coating in a drying oven for keeping the temperature at 40 ℃ for 2 hours, keeping the coating in a semi-solidified state, slowly drawing out the support bars to form hollow through holes which are penetrated vertically and horizontally, namely a microvascular network, finally, sealing and blocking the two ends of the longitudinal holes and one end of the transverse channel by the bottom layer coating, then placing a sample in the drying oven, keeping the temperature at 60 ℃ for 30min to fully solidify the bottom layer coating;
step 4, preparing and pouring a repairing agent: dissolving 100 parts of epoxy resin 618 in 10 parts of acetone, adding 10 parts of benzyl alcohol and 5 parts of pigment to prepare a repairing agent, injecting the repairing agent into the microvascular network obtained in the step 3 by using an injector, and then completely blocking the openings of the rest pores by using primer;
step 5, preparing and coating a surface layer coating: according to the mass of each component, 100 parts of epoxy resin E-44 is dissolved in 50 parts of acetone, 13 parts of ethylenediamine, 5 parts of pigment and 200 parts of modified nano SiO are added2Preparing a surface layer coating, uniformly spraying the surface layer coating on the surface of the bottom layer coating by using a spray gun to form a coating with the thickness of 0.3mm, and naturally curing at normal temperature to obtain the surface layer coating.
Example 4:
a preparation method of a microvascular self-repairing coating comprises the following steps:
step 1, surface modification of the filler: firstly, weighing a certain mass of pottery clay, heavy calcium carbonate, fly ash and nano SiO2As a filling material, respectively weighing a silane coupling agent KH-560 with the mass of 1.75% of that of the corresponding filling material, diluting the silane coupling agent KH-560 into a solution with the mass of 10% by using absolute ethyl alcohol, uniformly spraying the solution into the corresponding filling material under the condition of stirring, and drying the solution at the temperature of 60 ℃ for later use;
step 2, preparing a primer: according to the mass of each component, 100 parts of epoxy resin E-44 is dissolved in 60 parts of acetone solvent, 9 parts of diethylenetriamine and 3 parts of benzyl alcohol are added after the dissolution, 180 parts of modified quartz powder is added after the uniform stirring, the continuous stirring is carried out for 10-15 min, 80 parts of modified muscovite and 200 parts of modified calcium carbonate are sequentially added while the stirring is carried out, 20 parts of acetone is added to adjust the viscosity of the system, and the bottom coating is obtained after the full uniform stirring;
step 3, coating of a bottom layer coating and construction of a microvascular network: laying longitudinal and transverse support bars on the surface of a base material, wherein the diameter of the longitudinal support bars is 2mm, the interval is 20mm, the diameter of the transverse support bars is 1mm, and the interval is 13mm, then uniformly coating the bottom layer coating prepared in the step 2 on the surfaces of the base material and the support bars to form a coating with the thickness of 3-3.5 mm, then placing the coating in a drying oven for keeping the temperature at 40 ℃ for 2 hours, keeping the coating in a semi-cured state, slowly drawing out the support bars to form hollow through holes which are penetrated vertically and horizontally, namely a microvascular network, finally, sealing and blocking the two ends of the longitudinal holes and one end of the transverse channel by using the bottom layer coating, then placing a sample in the drying oven, keeping the temperature at 60 ℃ for 30min to fully cure the bottom layer coating;
step 4, preparing and pouring a repairing agent: dissolving 100 parts of epoxy resin 618 in 10 parts of acetone according to the mass of each component, adding 5 parts of benzyl alcohol and 5 parts of pigment to prepare a repairing agent, injecting the repairing agent into the microvascular network obtained in the step 3 by using an injector, and then completely plugging the openings of the rest pores by using primer;
step 5, preparing and coating a surface layer coating: according to the mass of each component, 100 parts of epoxy resin E-44 is dissolved in 50 parts of acetone, 12 parts of ethylenediamine, 7 parts of pigment and 150 parts of modified nano SiO are added2Preparing a surface layer coating, uniformly spraying the surface layer coating on the surface of the bottom layer coating by using a spray gun to form a coating with the thickness of 0.8mm, and naturally curing at normal temperature to obtain the surface layer coating.
3. Structure and performance of microvascular self-healing coating
Fig. 1 is a schematic structural diagram of a microvascular self-healing coating constructed in the present application, fig. 2 is a sample of the microvascular self-healing coating, fig. 3 is a local end face of the sample of the microvascular self-healing coating, and fig. 4 is an SEM image of partial healing of a healing agent overflowing from a scratch of the coating.
As can be seen from the structural schematic diagram of the microvascular self-repair coating in fig. 1, the microvascular self-repair coating is composed of a primer coating and a topcoat coating, a microvascular network system is located in the primer coating and is composed of an aorta and a capillary, the aorta is located inside the microvascular network, the capillary is located outside the microvascular network, an epoxy resin E-44 solution is injected into the microvascular network as a repair agent, an excessive amount of ethylenediamine contained in the topcoat coating is a curing agent, and a sample of the microvascular self-repair coating is shown in fig. 2. After the healing agent is injected into the interior of the microvascular network, the ends of the microvasculature are plugged with a primer, thereby sealing the interior of the microvasculature with the liquid healing agent, as shown in fig. 3. Compared with the primer coating, the surface coating is hard and brittle, and the thickness of the surface coating is only 0.3-0.8 mm, so that when the surface coating is damaged, capillary vessels of the primer coating can be scratched easily without injuring aorta, and thus the repairing agent can continuously overflow to the surface of the coating through a capillary network and can heal the wound through reaction with the excessive curing agent ethylenediamine in the surface coating, and as shown in fig. 4, the SEM image of the scratch of the coating partially repaired by the repairing agent is shown.
The invention constructs a microvascular network system in the coating and is filled with a repair agent. After the coating is damaged, the repairing agent overflows from the damaged surface through the microvascular network and reacts with the curing agent in the surface coating, so that the damaged coating is repaired. The microvascular self-repairing coating can automatically repair a damaged surface and has the capability of repairing at the same position for multiple times. The micro-vessel coating can be applied to the surface of a workpiece which is inconvenient to maintain or has higher maintenance cost, thereby prolonging the service life of the workpiece and reducing the comprehensive application cost.
The advantages of the invention are mainly embodied in three aspects: firstly, the construction of the microvascular channel is relatively simple; secondly, the microvascular self-repairing coating can realize multiple times of repairing of damage at the same position; thirdly, the replaceability of the repairing agent/curing agent is stronger, the application adaptability is stronger, and the preparation process is relatively simple.
The longitudinal microvasculature has large diameter and deep implantation, and plays a role of 'aorta'; the transverse capillary has small diameter and shallow implantation, and plays the role of capillary. When the coating is damaged, the repair efficiency of the coating is high, and multiple repairs at the same position can be realized.
Claims (7)
1. A preparation method of a microvascular self-repairing coating is characterized by comprising the following steps:
step 1, surface modification of the filler: firstly, certain mass of muscovite, heavy calcium carbonate, quartz powder and nano SiO are weighed2As a filler, respectively weighing a silane coupling agent KH-560 with the mass of 1.5-2% of that of the corresponding filler, diluting the silane coupling agent KH-560 into a solution with the mass of 5-10% by using absolute ethyl alcohol, uniformly spraying the solution into the corresponding filler under the stirring condition, and drying the solution at the temperature of 60 ℃ for later use;
step 2, preparing a primer: according to the mass of each component, 100 parts of epoxy resin E-44 is dissolved in 60-80 parts of acetone solvent, 9 parts of diethylenetriamine and 2-3 parts of benzyl alcohol are added after the dissolution, 150-200 parts of modified quartz powder are added after the uniform stirring, the continuous stirring is carried out for 10-15 min, 80-100 parts of modified muscovite and 200-300 parts of modified calcium carbonate are sequentially added while the stirring is carried out, 10-50 parts of acetone is added to adjust the viscosity of the system, and the bottom coating is obtained after the full and uniform stirring;
step 3, coating of a bottom layer coating and construction of a microvascular network: laying longitudinal and transverse support bars on the surface of a base material, wherein the diameter of the longitudinal support bars is 2mm, the interval is 20-30 mm, the diameter of the transverse support bars is 1mm, and the interval is 10-15 mm, then uniformly coating the bottom layer coating prepared in the step 2 on the surfaces of the base material and the support bars to form a coating with the thickness of 3-3.5 mm, then placing the coating in a drying box, keeping the temperature for 2 hours at 40 ℃, then keeping the bottom layer coating in a semi-solidified state, slowly drawing out the support bars to form hollow channels which penetrate through each other vertically and horizontally, namely a microvascular network, finally, plugging the two ends of the longitudinal channels and one end of the transverse channel with the bottom layer coating, then placing a sample in a drying box, keeping the temperature for 30min at 60 ℃ to fully solidify the bottom layer coating;
step 4, preparing and pouring a repairing agent: dissolving 100 parts of epoxy resin 618 in 10 parts of acetone, adding 5-10 parts of benzyl alcohol and 3-5 parts of pigment to prepare a repairing agent, injecting the repairing agent into the microvascular network obtained in the step 3 by using an injector, and then completely plugging the openings of the rest pore channels by using primer;
step 5, preparing and coating a surface layer coating: according to the mass of each component, 100 parts of epoxy resin E-44 is dissolved in 30-50 parts of acetone, 12-15 parts of ethylenediamine, 5-7 parts of pigment and 150-200 parts of modified nano SiO2Preparing a surface layer coating, uniformly spraying the surface layer coating on the surface of the bottom layer coating by using a spray gun to form a coating with the thickness of 0.3-0.8 mm, and naturally curing at normal temperature to obtain the surface layer coating.
2. The method for preparing the microvascular self-healing coating of claim 1The method is characterized in that the purity of the silane coupling agent KH-560 in the step 1 is analytical purity, the average grain diameter of the quartz powder and the muscovite is less than 15 mu m, and the nano SiO is2The average particle diameter of (A) is 20 to 80 nm.
3. The method for preparing the microvascular self-healing coating according to claim 1, wherein the purity of the epoxy resin E-44 of step 2 is chemically pure, and the purity of acetone, benzyl alcohol and diethylenetriamine is analytically pure.
4. The method of claim 1, wherein the epoxy resin 618 of step 4 is chemically pure.
5. The method for preparing the self-repairing coating for the microvasculature as claimed in claim 1, wherein the purity of the ethylenediamine in step 5 is analytical grade.
6. The preparation method of the microvascular self-healing coating according to claim 1, wherein the support bars in step 3 are rubber bars, iron wires or wood bars.
7. The preparation method of the microvascular self-healing coating according to claim 1, wherein in step 1 the muscovite filler is replaced with talc, china clay or bentonite, the ground calcium carbonate filler is replaced with light calcium carbonate, and the quartz powder filler is replaced with titanium dioxide or fly ash.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009029319A2 (en) * | 2007-06-08 | 2009-03-05 | The Board Of Trustees Of The University Of Illinois | Self-healing materials with microfluidic networks |
| CN105238211A (en) * | 2015-10-28 | 2016-01-13 | 陕西理工学院 | Preparation method for self-repairing coating material and application thereof |
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| US20130189888A1 (en) * | 2011-03-11 | 2013-07-25 | Jason F. Patrick | Self-Healing Composite Materials And Micro-Vascular Composites For Forming The Materials |
| US10081715B2 (en) * | 2013-11-14 | 2018-09-25 | The Board Of Trustees Of The University Of Illinois | Branched interconnected microvascular network in polymers and composites using sacrificial polylactide films, sheets and plates |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009029319A2 (en) * | 2007-06-08 | 2009-03-05 | The Board Of Trustees Of The University Of Illinois | Self-healing materials with microfluidic networks |
| CN105238211A (en) * | 2015-10-28 | 2016-01-13 | 陕西理工学院 | Preparation method for self-repairing coating material and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Self-Healing Materials with Interpenetrating Microvascular Networks";Christopher J. Hansen et al.;《Advanced materials》;20091231;第21卷;第434-4147页 * |
| "Self-healing materials with microvascular networks";KATHLEEN S. TOOHEY et al.;《nature materials》;20070610;第6卷;第581-585页 * |
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